Ab initio molecular dynamics investigation of the formyl cation in the superacid SbF5/HF

Simone Raugei; Michael L. Klein

doi:10.1021/jp0106855

Ab initio molecular dynamics investigation of the formyl cation in the superacid SbF5/HF

Simone Raugei, Michael L. Klein

Pacific Northwest National Laboratory

Research output: Contribution to journal › Article

20 Citations (Scopus)

Abstract

The formyl cation (HCO⁺) is an intermediate involved in electrophilic formylation reactions of aromatic compounds. We have employed ab initio molecular dynamics simulation to investigate free energy profiles along several possible reaction paths for CO in the SbF₅/HF superacid solution for different concentrations of SbF₅. The formation of the HCO⁺ cation is optimally favored in the 1:1 SbF₅/HF solution. However, no evidence has been found for the presence of either the isoformyl cation, COH⁺, or the protoformyl dication, HCOH²⁺. A novel mechanism for the experimentally observed fast proton exchange in the system CO in 1:1 SbF₅/HF is proposed.

Original language	English
Pages (from-to)	8212-8219
Number of pages	8
Journal	Journal of Physical Chemistry B
Volume	105
Issue number	34
DOIs	https://doi.org/10.1021/jp0106855
Publication status	Published - Aug 30 2001

Fingerprint

Carbon Monoxide

Molecular dynamics

Cations

Positive ions

molecular dynamics

cations

Aromatic compounds

Free energy

Protons

aromatic compounds

Ion exchange

Computer simulation

free energy

protons

profiles

oxomethylium

simulation

ASJC Scopus subject areas

Physical and Theoretical Chemistry

Cite this

Raugei, S., & Klein, M. L. (2001). Ab initio molecular dynamics investigation of the formyl cation in the superacid SbF5/HF. Journal of Physical Chemistry B, 105(34), 8212-8219. https://doi.org/10.1021/jp0106855

Ab initio molecular dynamics investigation of the formyl cation in the superacid SbF5/HF. / Raugei, Simone; Klein, Michael L.

In: Journal of Physical Chemistry B, Vol. 105, No. 34, 30.08.2001, p. 8212-8219.

Research output: Contribution to journal › Article

Raugei, S & Klein, ML 2001, 'Ab initio molecular dynamics investigation of the formyl cation in the superacid SbF5/HF', Journal of Physical Chemistry B, vol. 105, no. 34, pp. 8212-8219. https://doi.org/10.1021/jp0106855

Raugei S, Klein ML. Ab initio molecular dynamics investigation of the formyl cation in the superacid SbF5/HF. Journal of Physical Chemistry B. 2001 Aug 30;105(34):8212-8219. https://doi.org/10.1021/jp0106855

Raugei, Simone ; Klein, Michael L. / Ab initio molecular dynamics investigation of the formyl cation in the superacid SbF5/HF. In: Journal of Physical Chemistry B. 2001 ; Vol. 105, No. 34. pp. 8212-8219.

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10.1021/jp0106855